Resist underlayer film-forming composition containing naphthalene unit

Abstract

To provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, and to provide a resist pattern production method and a semiconductor device manufacturing method using the resist underlayer film-forming composition.SOLUTION: The resist underlayer film-forming composition contains: a reaction product of a compound (A) represented by the following formula (100) (where Ar1 and Ar2 each independently represent an optionally substituted C6-40 aromatic ring; at least one of Ar1 and Ar2 is a naphthalene ring; L1 represents a single bond, an optionally substituted C1-10 alkylene group or an optionally substituted C2-10 alkenylene group; T1 and T2 each independently represent a single bond, an ester bond or an ether bond; and E represents an epoxy group) and a compound (B) containing at least two groups reactive with epoxy groups; and a solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for use in lithography processes in semiconductor manufacturing, particularly in cutting-edge lithography processes (ArF, EUV, EB, etc.), and also to a method for producing a substrate having a resist pattern to which the resist underlayer film is applied, and a method for producing a semiconductor device. [Background technology]

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has been performed. The microfabrication is a processing method in which a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, and the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a device pattern is drawn, developed, and the substrate is etched using the obtained photoresist pattern as a protective film to form fine irregularities on the substrate surface corresponding to the pattern. In recent years, the integration density of semiconductor devices has increased, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to the influence of the semiconductor substrate and the like has become a major problem. In order to solve this problem, a method of providing a resist underlayer film between the resist and the semiconductor substrate has been widely considered. Patent Document 1 discloses a resist underlayer film forming composition for EUV lithography having a condensation polymer. Patent Document 2 discloses an organic film material for forming an organic film having both dry etching resistance and high-level embedding / planarization properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Patent Application Publication No. 2013 / 018802 [Patent Document 2] JP 2016-216367 A Summary of the Invention [Problem to be solved by the invention]

[0004] The properties required for the resist underlayer film include, for example, that intermixing with the resist film formed on the upper layer does not occur (that is, that the resist underlayer film is insoluble in a resist solvent).

[0005] In the case of lithography involving EUV exposure, the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is formed to be thinner than conventional films. When forming such a thin film, pinholes and aggregation are likely to occur due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0006] On the other hand, in forming a resist pattern, in a negative development process in which an unexposed portion of the resist film is removed using a solvent capable of dissolving the resist film, usually an organic solvent, in a development step, and the exposed portion of the resist film is left as a resist pattern, or in a positive development process in which the exposed portion of the resist film is removed, and the unexposed portion of the resist film is left as a resist pattern, improvement of the adhesion of the resist pattern is a major issue.

[0007] There is also a demand for suppressing deterioration of LWR (Line Width Roughness) during resist pattern formation, forming resist patterns with good rectangular shapes, and improving resist sensitivity.

[0008] An object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, which has solved the above-mentioned problems, and a method for forming a resist pattern using the resist underlayer film-forming composition. [Means for solving the problem]

[0009] The present invention encompasses the following:

[0010] [1] The following formula (100): [ka] (In formula (100), Ar 1 and Ar 2 each independently represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and Ar 1 and Ar 2 At least one of L is a naphthalene ring; 1 represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; T 1 and T 2 each independently represents a single bond, an ester bond or an ether bond, and E represents an epoxy group; A resist underlayer film-forming composition comprising a reaction product of a compound (B) having at least two groups reactive with an epoxy group, and a solvent.

[0011] [2] The resist underlayer film forming composition according to [1], wherein the compound (B) contains a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

[0012] [3] The compound (B) is represented by the following formula (101): [ka] (In formula (101), X 1 is represented by the following formula (2), formula (3), formula (4) or formula (0): [ka] (In formulas (2), (3), (4) and (0), R 1 and R 2each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the benzyl group, and the phenyl group are each substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 10 carbon atoms. The resist underlayer film forming composition according to [1] or [2], wherein R1 and R2 may be bonded to each other to form a ring having 3 to 10 carbon atoms, R3 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 10 carbon atoms.

[0013] [4] The terminal of the reaction product is represented by the following formula (102): [ka] In formula (102), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 1 represents an ester bond, an ether bond, or an optionally substituted alkenylene group having 2 to 10 carbon atoms, 1 each independently represents a group selected from the group consisting of a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms, n represents an integer of 0 to 5, and * represents a bonding portion to the reaction product. The resist underlayer film forming composition according to any one of the items [1] to [3],

[0014] [5] The resist underlayer film forming composition according to any one of [1] to [4], further comprising an acid generator.

[0015] [6] The resist underlayer film forming composition according to any one of [1] to [5], further comprising a crosslinking agent.

[0016] [7] The resist underlayer film forming composition according to any one of items [1] to [6], which is used in an EUV (extreme ultraviolet) exposure process.

[0017] [8] A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film forming composition according to any one of [1] to [7].

[0018] [9] A step of applying the resist underlayer film forming composition according to any one of items [1] to [7] onto a semiconductor substrate and baking the composition to form a resist underlayer film; A step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

[0019]

[10] forming a resist underlayer film on a semiconductor substrate, the resist underlayer film being composed of the resist underlayer film forming composition according to any one of [1] to [7]; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; processing a semiconductor substrate using the patterned resist underlayer film; A method for manufacturing a semiconductor device, comprising: Effect of the Invention

[0020] The resist underlayer film forming composition of the present invention has excellent coatability to a semiconductor substrate to be processed by containing a naphthalene ring unit in the polymer, and has excellent adhesion at the interface between the resist and the resist underlayer film during resist pattern formation, so that peeling of the resist pattern does not occur, deterioration of LWR (Line Width Roughness, line width roughness, line width fluctuation (roughness)) during resist pattern formation can be suppressed, the resist pattern size (minimum CD size) can be minimized, and a good resist pattern with a rectangular shape can be formed. This effect is particularly remarkable when EUV (wavelength 13.5 nm) or EB (electron beam) is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] <Resist underlayer film forming composition> The resist underlayer film forming composition of the present invention has the following formula (100): [ka] (In formula (100), Ar 1 and Ar 2 each independently represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and Ar 1 and Ar 2 At least one of L is a naphthalene ring; 1 represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; T 1 and T 2 each independently represents a single bond, an ester bond or an ether bond, and E represents an epoxy group.) and a compound (B) containing at least two groups reactive with an epoxy group, and a solvent.

[0022] By reacting the compound (A) with the compound (B) by a known method, for example, as described in the Examples, a reaction product (polymer) of the compound (A) and the compound (B) can be produced.

[0023] Examples of the aromatic ring having 6 to 40 carbon atoms include benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, and dibenzo[a,j]anthracene.

[0024] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 1-ethyl-n-propylene group, a 2,2-dimethyl ...2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 2,2-dimethyl propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl-cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene , 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4-dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,Examples of the cyclopropylene group include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0025] Examples of the alkenylene group having 2 to 10 carbon atoms include the alkylene groups having 2 to 10 carbon atoms and having at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms. Of the alkenylene groups having 2 to 10 carbon atoms, a vinylene group is preferred.

[0026] The above term "optionally substituted" means that some or all of the hydrogen atoms present in the alkylene group having 1 to 10 carbon atoms or the alkenylene group having 2 to 10 carbon atoms may be substituted with, for example, a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0027] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2 -dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, and decyl group.

[0028] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group and n-decanyloxy group.

[0029] The compound (A) may be a commercially available compound having at least two epoxy groups containing a naphthalene structure that exhibits the effects of the present invention, and specific examples include EPICLON HP-4770, HP-6000, and WR-600 (all manufactured by DIC Corporation).

[0030] Furthermore, as the compound (A), a compound having two epoxy groups and having the following general formula described in JP-A-2007-262013 may be used. [ka] (In formula (3), R 3 represents a hydrogen atom or a methyl group, each Ar independently represents a naphthylene group, a phenylene group, or a naphthylene group or a phenylene group having an alkyl group having 1 to 4 carbon atoms or a phenyl group as a substituent, R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n and m each represent an integer of 0 to 2, and either n or m is 1 or more, R 1 represents a hydrogen atom or an epoxy group-containing aromatic hydrocarbon group represented by the following general formula (3-2), in which the total number of aromatic nuclei is 2 to 8. In addition, in general formula (3), the bonding position to the naphthalene skeleton may be either of the two rings constituting the naphthalene ring. [ka] (In general formula (3-2), R 3 represents a hydrogen atom or a methyl group, each Ar independently represents a naphthylene group, a phenylene group, or a naphthylene group or phenylene group having an alkyl group having 1 to 4 carbon atoms or a phenyl group as a substituent, and p is an integer of 1 or 2. The compound represented by the above formula (100) and the above general formula (3) may be contained in a solid content of the resist underlayer film forming composition of the present invention in an amount of, for example, 10 mass % or more, 30 mass % or more, or 50 mass % or more.

[0031] Specific examples of the compound (B) containing at least two groups reactive with an epoxy group include the compounds shown below. [ka] [ka]

[0032] The compound (B) may contain a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

[0033] Examples of the heterocyclic structure include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazinone, triazinedione, and triazinetrione.

[0034] The heterocyclic structure may be a structure derived from a barbituric acid.

[0035] The aromatic ring structure having 6 to 40 carbon atoms is as described above.

[0036] The compound (B) is represented by the following formula (101): [ka] (In formula (101), X 1 is represented by the following formula (2), formula (3), formula (4) or formula (0): [ka] (In formulas (2), (3), (4) and (0), R 1 and R 2each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the benzyl group, and the phenyl group are each substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 10 carbon atoms. Alternatively, R1 and R2 may be bonded to each other to form a ring having 3 to 10 carbon atoms, R3 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 10 carbon atoms.

[0037] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0038] Examples of the alkylthio group having 1 to 10 carbon atoms include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a nonylthio group, and a decanylthio group.

[0039] Examples of the ring having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane. The meanings of the other terms are as described above.

[0040] The terminal of the reaction product is represented by the following formula (102): [ka] In formula (102), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 1 represents an ester bond, an ether bond, or an optionally substituted alkenylene group having 2 to 10 carbon atoms, 1 independently represent a group selected from the group consisting of a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms, n represents an integer of 0 to 5, and * represents a bonding portion to the reaction product.) may be included at the terminal. The meanings of each term are as described above.

[0041] The structure represented by the formula (1-2) may be derived from cinnamic acid or salicylic acid which may be substituted with a halogen atom.

[0042] Examples of compounds that can be bonded to the terminal of the reaction product to derive the structure represented by formula (1-2) include compounds represented by the following formulas. [ka] [ka]

[0043] The end of the reaction product may have an aliphatic ring structure in which the carbon-carbon bond may be interrupted by a heteroatom and may be substituted with a substituent, as described in WO2020 / 226141.

[0044] The aliphatic ring may be a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

[0045] The polycyclic aliphatic ring may be a bicyclic or tricyclic ring.

[0046] The aliphatic ring may have at least one unsaturated bond.

[0047] The substituent of the aliphatic ring may be selected from a hydroxy group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and a carboxy group.

[0048] Specific examples of the compound for inducing an aliphatic ring structure, in which the carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent, at the end of the reaction product include compounds having the structures shown below. [ka] [ka] [ka]

[0049] Furthermore, the terminal of the reaction product may have a structure represented by the following formula (1) described in WO2012 / 124597. [ka] (In the formula, R1, R2, and R3 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group; at least one of R1, R2, and R3 is the hydrocarbon group; m and n each independently represent 0 or 1; and the main chain of the polymer is bonded to a methylene group when n represents 1, or is bonded to a group represented by -O- when n represents 0.)

[0050] Furthermore, the terminal of the reaction product may have a structure represented by the following formula (1a), formula (1b), or formula (2) described in WO2013 / 168610. [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group, a phenyl group, a benzyl group, a benzyloxy group, a benzylthio group, an imidazole group, or an indole group, and the hydrocarbon group, the alicyclic hydrocarbon group, the phenyl group, the benzyl group, the benzyloxy group, the benzylthio group, the imidazole group, or the indole group may have at least one hydroxy group or methylthio group as a substituent, R4 represents a hydrogen atom or a hydroxy group, Q1 represents an arylene group, v represents 0 or 1, y represents an integer of 1 to 4, w represents an integer of 1 to 4, x1 represents 0 or 1, and x2 represents an integer of 1 to 5.)

[0051] Furthermore, the terminal of the reaction product may have a structure represented by the following formula (1) described in WO2015 / 046149. [ka] (In the formula, R1, R2, and R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 13 carbon atoms, a halogeno group, or a hydroxy group, at least one of R1, R2, and R3 represents the alkyl group, Ar represents a benzene ring, a naphthalene ring, or an anthracene ring, the two carbonyl groups are each bonded to two adjacent carbon atoms of the ring represented by Ar, and X represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have an alkoxy group having 1 to 3 carbon atoms as a substituent.)

[0052] Furthermore, the terminal of the reaction product may have a structure represented by the following formula (1) or formula (2) described in WO2015 / 163195 at the terminal of the polymer chain. [ka] (In the formula, R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a halogeno group or a hydroxy group which may have a substituent; R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogeno group or an ester group represented by -C(=O)OX; X represents an alkyl group having 1 to 6 carbon atoms, which may have a substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group or a halogeno group; R4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms; R5 represents a divalent organic group having 1 to 8 carbon atoms; A represents an aromatic ring or an aromatic heterocycle; t represents 0 or 1; and u represents 1 or 2.)

[0053] In addition, the terminal of the reaction product may have a structure represented by the following formula (1) or (2) described in WO2020 / 071361. [ka] (In the above formulas (1) and (2), X is a divalent organic group, A is an aryl group having 6 to 40 carbon atoms, R1 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R2 and R3 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 40 carbon atoms which may be substituted, n1 and n3 are each independently an integer of 1 to 12, and n2 is an integer of 0 to 11.)

[0054] The entire disclosures of WO2020 / 226141, WO2012 / 124597, WO2013 / 168610, WO2015 / 046149, WO2015 / 163195 and WO2020 / 071361 are incorporated by reference into this application.

[0055] The lower limit of the weight average molecular weight of the reaction product (polymer), measured by gel permeation chromatography, for example, as described in the Examples, is, for example, 1,000 or 2,000, and the upper limit of the weight average molecular weight of the reaction product is, for example, 30,000, 20,000, or 10,000.

[0056] The resist underlayer film forming composition of the present invention may be an EUV resist underlayer film forming composition used in an EUV (extreme ultraviolet) exposure process.

[0057] <Solvent> The solvent used in the resist underlayer film forming composition of the present invention is not particularly limited as long as it can uniformly dissolve the solid components contained therein at room temperature, such as the polymer, but is preferably an organic solvent generally used in chemical solutions for semiconductor lithography processes.Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexane ... Examples of the solvent include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0058] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0059] <Acid generator> The acid generator contained in the resist underlayer film forming composition of the present invention as an optional component can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator.The thermal acid generator can be, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridinium salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and other sulfonic acid compounds and carboxylic acid compounds.

[0060] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0061] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0062] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0063] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0064] The acid generators may be used alone or in combination of two or more.

[0065] When the acid generator is used, the content of the acid generator is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass, relative to the crosslinking agent described below.

[0066] <Crosslinking agent> Examples of the crosslinking agent contained as an optional component in the resist underlayer film forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK (registered trademark) 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0067] In addition, the crosslinking agent of the present application may be a nitrogen-containing compound having, in one molecule, 2 to 6 substituents bonded to nitrogen atoms and represented by the following formula (1d), as described in WO 2017 / 187969.

[0068] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0069] [ka] (In formula (1E), the four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulae (1E-1) to (1E-6).

[0070] [ka]

[0071] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents bonded to a nitrogen atom in one molecule represented by the following formula (2d) with at least one compound represented by the following formula (3d).

[0072] [ka] (In formula (2d) and formula (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.) The glycoluril derivative represented by the formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).

[0073] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).

[0074] [ka] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represent an alkyl group having 1 to 4 carbon atoms.) Examples of the glycoluril derivative represented by the formula (2E) include the compounds represented by the following formulae (2E-1) to (2E-4). Furthermore, examples of the compound represented by the formula (3d) include the compounds represented by the following formulae (3d-1) and (3d-2).

[0075] [ka] [ka]

[0076] With regard to the content of the nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) bonded to the nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0077] The crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2) described in WO 2014 / 208542.

[0078] [ka] (In the formula, Q 1 represents a single bond or m represents a monovalent organic group, R 1 and R 4 each represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R 2 and R 5 each represents a hydrogen atom or a methyl group, and R 3 and R 6 respectively represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n1 indicates an integer satisfying 1≦n1≦3, n2 indicates an integer satisfying 2≦n2≦5, n3 indicates an integer satisfying 0≦n3≦3, n4 indicates an integer satisfying 0≦n4≦3, and 3≦(n1+n2+n3+n4)≦6. n5 is an integer satisfying 1≦n5≦3, n6 is an integer satisfying 1≦n6≦4, n7 is an integer satisfying 0≦n7≦3, n8 is an integer satisfying 0≦n8≦3, and 2≦(n5+n6+n7+n8)≦5. m1 represents an integer from 2 to 10.

[0079] The crosslinkable compound represented by the above formula (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0080] [ka] (In the formula, Q 2 R represents a single bond or a divalent organic group. 8 , R 9 , R 11 and R 12 each represents a hydrogen atom or a methyl group, and R 7 and R 10 respectively represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n9 indicates an integer satisfying 1≦n9≦3, n10 indicates an integer satisfying 2≦n10≦5, n11 indicates an integer satisfying 0≦n11≦3, n12 indicates an integer satisfying 0≦n12≦3, and 3≦(n9+n10+n11+n12)≦6. n13 indicates an integer satisfying 1≦n13≦3, n14 indicates an integer satisfying 1≦n14≦4, n15 indicates an integer satisfying 0≦n15≦3, n16 indicates an integer satisfying 0≦n16≦3, and 2≦(n13+n14+n15+n16)≦5. m2 represents an integer from 2 to 10.

[0081] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] Examples of the compounds represented by formula (G-3) and formula (G-4) include the following.

[0088] [ka]

[0089] [ka] In the formula, Me represents a methyl group.

[0090] The entire disclosure of WO 2014 / 208542 is incorporated by reference into this application.

[0091] When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass, relative to the reaction product.

[0092] <Other ingredients> A surfactant may be further added to the resist underlayer film forming composition of the present invention in order to prevent pinholes, striations, etc., and to further improve coating properties against surface unevenness. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and the like. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as F-TOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0093] The solid content of the resist underlayer film forming composition of the present invention, that is, the content of components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.

[0094] <Resist Underlayer Film> The resist underlayer film according to the present invention can be produced by applying the above-mentioned resist underlayer film-forming composition onto a semiconductor substrate and baking it.

[0095] Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0096] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin-coating (spin-on glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0097] The resist underlayer film forming composition of the present invention is applied onto such a semiconductor substrate by a suitable application method such as a spinner or coater. Then, the composition is baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. The baking temperature is preferably 120°C to 350°C, the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C, and the baking time is 0.8 minutes to 10 minutes.

[0098] The thickness of the resist underlayer film to be formed may be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5 nm) to 0.05 μm (50 nm), ) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), 0.004 μm (4 nm), 0.005 μm (5 nm). If the baking temperature is lower than the above range, crosslinking is insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may be decomposed by heat.

[0099] <Method for manufacturing a patterned substrate and a semiconductor device> The manufacturing method of the patterned substrate is as follows. Usually, a photoresist layer is formed on a resist underlayer film. The photoresist formed by coating and baking on the resist underlayer film by a method known per se is not particularly limited as long as it is sensitive to the light used for exposure. Either a negative photoresist or a positive photoresist can be used. There are positive photoresists consisting of a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with an acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low molecular compound that decomposes with an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists consisting of a binder having a group that decomposes with an acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley & Sons, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples of such photoresists include fluorine atom-containing polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0100] In addition, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., resist compositions, radiation-sensitive resin compositions, high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0101] Examples of the resist composition include the following compositions.

[0102] An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is eliminated by the action of an acid; and a compound represented by general formula (21).

[0103] [ka] In the general formula (21), m represents an integer of 1 to 6.

[0104] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0105] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0106] L2 represents an alkylene group which may have a substituent or a single bond.

[0107] W1 represents a cyclic organic group which may have a substituent.

[0108] M + represents a cation.

[0109] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, the metal element constituting the compound belonging to Period 3 to Period 7 of Groups 3 to 15 of the periodic table.

[0110] A radiation-sensitive resin composition comprising: a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group; and an acid generator.

[0111] [ka] In formula (31), Ar is a group in which (n+1) hydrogen atoms have been removed from an arene having 6 to 20 carbon atoms. 1 is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R 1 are the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 3 R is a monovalent group having 1 to 20 carbon atoms containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0112] A resist composition comprising: a resin (A1) that contains a structural unit having a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit having an acid labile group; and an acid generator.

[0113] [ka] [In formula (II), R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X 1 is a single bond, -CO-O-* or -CO-NR 4 -*, * represents a bond to -Ar, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxyl group and a carboxyl group.]

[0114] Examples of the resist film include the following.

[0115] A resist film comprising a base resin containing a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain upon exposure:

[0116] [ka] (In formula (a1) and formula (a2), R A R is each independently a hydrogen atom or a methyl group. 1 and R 2 R are each independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 are each independently a fluorine atom or a methyl group, and m is an integer of 0 to 4. 1 X is a single bond, a phenylene group, a naphthylene group, or an ester bond, a lactone ring, a phenylene group, or a naphthylene group. X 2 is a single bond, an ester bond, or an amide bond.

[0117] Examples of resist materials include the following:

[0118] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or formula (b2):

[0119] [ka] (In formula (b1) and formula (b2), R A is a hydrogen atom or a methyl group. 1 is a single bond or an ester group. 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, a part of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group, and X 2 At least one hydrogen atom in X is replaced with a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, and a part of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 may combine to form a carbonyl group. 1 ~R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms in these groups may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group or a sulfonate ester group. 1 and R 2 may combine to form a ring together with the sulfur atom to which they are attached.

[0120] A resist material comprising a base resin that includes a polymer containing a repeating unit represented by the following formula (a):

[0121] [ka] (In formula (a), R A R is a hydrogen atom or a methyl group. 1 R is a hydrogen atom or an acid labile group. 2 X is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 X is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. 2 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. n is an integer of 0 to 3. A resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid, The composition contains a base component (A) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) that is decomposable in an alkaline developer, The resist composition, wherein the fluorine additive component (F) contains a fluorine resin component (F1) having a structural unit (f1) containing a base dissociable group, and a structural unit (f2) containing a group represented by the following general formula (f2-r-1):

[0122] [ka] [In formula (f2-r-1), Rf 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0123] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0124] [ka] In formulae (f1-1) and (f1-2), R is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable site. aryl X is a divalent aromatic cyclic group which may have a substituent. 01 R is a single bond or a divalent linking group. 2 each independently represents an organic group having a fluorine atom.

[0125] Coatings, coating solutions, and coating compositions include, for example:

[0126] A coating comprising a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0127] An inorganic oxo / hydroxyl-based composition.

[0128] A coating solution comprising an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, a first organometallic composition; and a hydrolyzable metal compound represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof), a coating solution comprising a hydrolyzable metal compound.

[0129] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom, a coating solution.

[0130] An inorganic pattern-forming precursor aqueous solution comprising a mixture of water, a metal oxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0131] The exposure is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used, but the resist underlayer film forming composition of the present application is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more preferably for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C, and the development time is appropriately selected from 10 seconds to 300 seconds. As the alkaline developer, for example, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like can be added to these developers. Instead of the alkaline developer, a method of developing with an organic solvent such as butyl acetate to develop the parts of the photoresist where the alkaline dissolution rate is not improved can be used. Through the above steps, a substrate on which the resist is patterned can be manufactured.

[0132] Next, the resist underlayer film is dry etched using the formed resist pattern as a mask. In this case, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the substrate is processed by a method known per se (e.g., dry etching method) to manufacture a semiconductor device. EXAMPLES

[0133] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these.

[0134] The weight average molecular weights of the polymers shown in the following Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). For the measurement, a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions etc. are as follows.

[0135] GPC column: TSKgel Super-MultiporeHZ-N (2 columns) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0136] <Synthesis Example 1> In a reaction vessel, 7.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 1.92 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), 1.43 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 49.10 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 1. When GPC analysis was performed, the obtained polymer 1 had a weight average molecular weight of 3,200 and a dispersity of 3.7 in terms of standard polystyrene. The structure present in polymer 1 is shown in the following formula. [ka]

[0137] <Synthesis Example 2> In a reaction vessel, 25.00 g of EPICLON WR-600 (manufactured by DIC Corporation, propylene glycol monomethyl ether solution), 2.46 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Co., Ltd.), 1.84 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.40 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 11.21 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 2. When GPC analysis was performed, the obtained polymer 2 had a weight average molecular weight of 4,900 and a dispersity of 3.5 in terms of standard polystyrene.

[0138] <Synthesis Example 3> In a reaction vessel, 4.50 g of EPICLON HP-4770 (manufactured by DIC Corporation), 1.83 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), 0.33 g of trans-cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.28 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 85.54 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 3. When GPC analysis was performed, the obtained polymer 3 had a weight average molecular weight of 3,400 and a dispersity of 3.2 in terms of standard polystyrene. The structure present in polymer 3 is shown in the following formula. [ka]

[0139] <Synthesis Example 4> In a reaction vessel, 6.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 2.30 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), 0.65 g of trans-cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.37 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 83.97 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 4. When GPC analysis was performed, the obtained polymer 4 had a weight average molecular weight of 4,000 and a dispersity of 3.4 in terms of standard polystyrene. The structure present in polymer 4 is shown in the following formula. [ka]

[0140] <Synthesis Example 5> In a reaction vessel, 7.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 2.53 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), 1.02 g of trans-cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.44 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 76.87 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 5. When GPC analysis was performed, the obtained polymer 5 had a weight average molecular weight of 4,300 and a dispersity of 3.4 in terms of standard polystyrene. The structure present in polymer 5 is shown in the following formula. [ka]

[0141] <Synthesis Example 6> In a reaction vessel, 16.00 g of EPICLON WR-600 (DIC Corporation, propylene glycol monomethyl ether solution), 1.66 g of 5,5-diethylbarbituric acid (Tateyama Chemical Industry Co., Ltd.), 0.30 g of trans-cinnamic acid (Tokyo Chemical Industry Co., Ltd.), and 0.26 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added and dissolved in 76.03 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 6. When GPC analysis was performed, the obtained polymer 6 had a weight average molecular weight of 4,500 and a dispersity of 2.8 in terms of standard polystyrene.

[0142] <Synthesis Example 7> In a reaction vessel, 20.00 g of EPICLON WR-600 (DIC Corporation, propylene glycol monomethyl ether solution), 1.97 g of 5,5-diethylbarbituric acid (Tateyama Chemical Industry Co., Ltd.), 0.56 g of trans-cinnamic acid (Tokyo Chemical Industry Co., Ltd.), and 0.32 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added and dissolved in 66.22 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 7. When GPC analysis was performed, the obtained polymer 7 had a weight average molecular weight of 4,500 and a dispersity of 2.8 in terms of standard polystyrene.

[0143] <Synthesis Example 8> In a reaction vessel, 20.00 g of EPICLON WR-600 (DIC Corporation, propylene glycol monomethyl ether solution), 1.85 g of 5,5-diethylbarbituric acid (Tateyama Chemical Industry Co., Ltd.), 0.74 g of trans-cinnamic acid (Tokyo Chemical Industry Co., Ltd.), and 0.32 g of tetrabutylphosphonium bromide (Hokko Chemical Industry Co., Ltd.) were added and dissolved in 66.85 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 8. When GPC analysis was performed, the obtained polymer 8 had a weight average molecular weight of 3,700 and a dispersity of 2.6 in terms of standard polystyrene.

[0144] <Synthesis Example 9> In a reaction vessel, 3.17 g of EPICLON HP-4770 (manufactured by DIC Corporation), 1.22 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), 0.52 g of 9-anthracenecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.10 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added and dissolved in 45.00 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 9. When GPC analysis was performed, the obtained polymer 9 had a weight average molecular weight of 6,000 and a dispersity of 3.6 in terms of standard polystyrene.

[0145] <Synthesis Example 10> In a reaction vessel, 11.08 g of EPICLON WR-600 (DIC Corporation, propylene glycol monomethyl ether solution), 1.09 g of 5,5-diethylbarbituric acid (Tateyama Chemical Industry Co., Ltd.), 0.46 g of 9-anthracenecarboxylic acid (Tokyo Chemical Industry Co., Ltd.), and 0.09 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added and dissolved in 37.27 g of propylene glycol monomethyl ether. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 10. When GPC analysis was performed, the obtained polymer 10 had a weight average molecular weight of 6,300 and a dispersity of 2.9 in terms of standard polystyrene.

[0146] <Comparative Synthesis Example 1> In a reaction vessel, 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), and 4.1 g of benzyl triethylammonium chloride were added and dissolved in 682.00 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing comparative polymer 1. When GPC analysis was performed, the comparative polymer 1 obtained had a weight average molecular weight of 6,800 and a dispersity of 4.8 in terms of standard polystyrene. The structure present in comparative polymer 1 is shown in the following formula. [ka]

[0147] (Preparation of resist underlayer film) (Examples and Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in the above Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 were mixed in the ratios shown in Tables 1 and 2, and filtered through a fluororesin filter having a pore size of 0.1 μm to prepare solutions of compositions for forming resist underlayer films.

[0148] In Tables 1 and 2, tetramethoxymethyl glycoluril is abbreviated as PL-LI, imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, surfactant as R-30N, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amounts of each additive are shown in parts by mass. [Table 1] [Table 2]

[0149] (Photoresist solvent elution test) Each of the resist underlayer film forming compositions of Examples 1 to 10 and Comparative Example 1 was applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205° C. for 60 seconds to obtain a film with a thickness of 4 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether=70 / 30, which is a solvent used in photoresists, and the results are shown in Table 3, with a film thickness change of less than 5 Å being considered good and a film thickness change of 5 Å or more being considered bad. [Table 3]

[0150] (Resist patterning evaluation) [Resist pattern formation test using an electron beam lithography device] The resist underlayer film forming composition was applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a film thickness of 4 nm. A positive resist solution for EUV was spin-coated onto the resist underlayer film, and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under predetermined conditions using an electron beam lithography device (ELS-G130). After exposure, the film was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle development was performed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern.

[0151] The photoresist patterns thus obtained were evaluated for the possibility of forming 22 nm line and space (L / S). Formation of a 22 nm L / S pattern was confirmed in Examples 1 to 2, 4, and 7. The charge amount that formed a 22 nm line / 44 nm pitch (line and space (L / S=1 / 1)) was defined as the optimal irradiation energy, and the irradiation energy (μC / cm 2 ) and LWR are shown in Table 4. In Examples 1 to 2, 4, and 7, improvements in LWR and minimum CD size were confirmed compared to Comparative Example 1. [Table 4] [Industrial Applicability]

[0152] The resist underlayer film-forming composition according to the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, as well as a method for producing a substrate having a resist pattern and a method for producing a semiconductor device using the resist underlayer film-forming composition.

Claims

1. A compound of the following formula (100): 【Chemistry 1】 (In formula (100), Ar １ and Ar ２ each independently represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and Ar １ and Ar ２ at least one of L is a naphthalene ring; １ represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; T １ and T ２ each independently represents a single bond, an ester bond or an ether bond, and E represents an epoxy group; a step of applying and baking a resist underlayer film-forming composition containing a reaction product of a compound (B) containing at least two groups reactive with an epoxy group and a solvent, to form a resist underlayer film; a step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

2. A method for producing a patterned substrate as described in claim 1, wherein the compound (B) contains a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

3. The compound (B) is represented by the following formula (101): 【Chemistry 2】 In formula (101), X 1 represents the following formula (2), formula (3), formula (4), or formula (0): 【Transformation 3】 (In formulas (2), (3), (4), and (0), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, a carboxyl group, and an alkylthio group having 1 to 10 carbon atoms; and R 1 and R 2 may be bonded to each other to form a ring having 3 to 10 carbon atoms; and R 3 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 10 carbon atoms.

4. The terminal of the reaction product has the following formula (102): 【Chemistry 4】 4. The method for producing a patterned substrate according to claim 1, comprising a structure represented by the following formula: (in formula (102), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted; L 1 represents an ester bond, an ether bond, or an alkenylene group having 2 to 10 carbon atoms which may be substituted; n instances of R 1 independently represent a group selected from the group consisting of a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 10 carbon atoms which may be substituted, and an alkoxy group having 1 to 10 carbon atoms which may be substituted; n represents an integer of 0 to 5; and * represents the bonding site to the reaction product).

5. A method for producing a patterned substrate described in any one of claims 1 to 4, wherein the resist underlayer film forming composition further contains an acid generator.

6. A method for producing a patterned substrate described in any one of claims 1 to 5, wherein the resist underlayer film forming composition further contains a crosslinking agent.

7. A method for producing a patterned substrate according to any one of claims 1 to 6, wherein the resist underlayer film forming composition is used in an EUV (extreme ultraviolet) exposure process.

8. A resist underlayer film, characterized in that it is a fired product of a coating film made of the resist underlayer film forming composition described in claim 1.

9. A compound of the following formula (100): 【Transformation 5】 (in formula (100), Ar 1 and Ar 2 each independently represent an aromatic ring having 6 to 40 carbon atoms which may be substituted, and at least one of Ar 1 and Ar 2 is a naphthalene ring; L 1 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted; T 1 and T 2 each independently represent a single bond, an ester bond, or an ether bond; and E represents an epoxy group); forming a resist underlayer film from a resist underlayer film-forming composition containing a reaction product of a compound (B) containing at least two groups reactive with an epoxy group, and a solvent; forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; processing a semiconductor substrate using the patterned resist underlayer film; A method for manufacturing a semiconductor device, comprising:

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